1. Field of Invention
An engine with reduced carbon oxide emissions is conditioned by the presence lithium during the combustion process of hydrocarbon fuel containing lithium followed by continued reduced carbon oxide emissions during the combustion process of hydrocarbon fuel without additional lithium. This invention also relates to a method of combusting a hydrocarbon fuel in a hydrocarbon powered engine having an internal surface conditioned by combusting a hydrocarbon fuel containing a lithium salt to provide a lithium conditioned surface, wherein the effluent gas has a lower concentration of carbon oxides than combusting the fuel under similar conditions in an engine not having a lithium conditioned surface.
The additive contemplated for use in the present invention includes lithium salts, specifically lithium nitrate, in organic solvents including isopropanol. Metallic salt additives to engine fuels have been reported to increase internal combustion engine efficiency and decrease vehicle gaseous emissions such as CO, CO2, C6+, and other compounds. These phenomena are not completely understood and are dependent on many parameters including the fuel chemical composition and interaction as well as exposed physical environment.
The engines contemplated for use in the present invention include the gasoline-powered internal combustion engines ignited by spark and also compression internal combustion (diesel) engines.
The emissions analyses contemplated for use in the present invention are defined by the Gas Processors Association “Analysis for Natural Gas & Similar Gaseous Mixtures by Gas Chromatography” #2261 is Incorporated by Reference. Compounds contemplated for use in the present invention include CO2, C6+, and N2. Alkanes and other organic compounds are grouped together under unit measurement C6+ hexanes. Carbon oxides are carbon and oxygen containing compounds COx, where x=1, 2 . . . therefore, carbon monoxide and carbon dioxide are carbon oxides.
2. State of the Art
In the United States, the Environmental Protection Agency (EPA) regulates, monitors, and reports on many measurements of gases and chemicals used in vehicles. For example, the measurements may be reported by the EPA as: carbon content per gallon of gasoline, trends in carbon dioxide emissions, fuel economy, and technology usage, grams per mile, grams/mile values for total HC, CO, CO2, CH3, OH, HCHO, NMHC, CH4, specific gravity, carbon weight fraction, net heating value, and natural gas. Monitoring and reduction of emissions of gaseous compounds by industrial applications is required by many government entities.
In order to comply with requirements in the Clean Air Act and California's Low Emission Vehicle/Clean Fuels Program, vehicle emissions are monitored and reduced. Additives may have beneficial effects on reducing vehicle emissions content including gasoline aromatics, olefin, sulfur, and carbon oxides. The United States Environmental Protection Agency, Transportation and Air Quality, monitors and regulates gasoline and diesel fuels. International, U.S. Government, and California policies and concerns focus on combustion efficiency and emissions of carbon oxides. Emission facts from the U.S. Environmental Protection Agency Code of Federal Regulations (40 CFR 600.113) provides values for carbon content per gallon of gasoline and diesel fuel used to calculate fuel economy of vehicles:    Gasoline carbon content per gallon: 2,421 grams    Diesel carbon content per gallon: 2,778 grams
The EPA summarized key trends in carbon dioxide emissions, fuel economy, and technology usage related to model year (MY) 1975 through 2009 light-duty vehicles sold in the United States. The first CO2 emissions data are included in the EPA 2009 report. For model year 2009, EPA projects average real-world CO2 emissions to be 422 grams per mile and fuel economy to be 21.1 miles per gallon. (Vehicles Light-Duty Automotive Technology, Carbon Dioxide Emissions, and Fuel Economy Trends: 1975 Through 2009, EPA-420-R-09-0 14, 1118-2009).
U.S. Environmental Protection Agency fuel economy calculation procedures are set forth in the Code of Federal Regulations Title 40, Volume 27, Part 600, Subpart B, Section 600.113-93 for all official EPA testing of motor vehicles fueled with gasoline, diesel, methanol or natural gas. The EPA Green Vehicle Guide scores cars and trucks based on tailpipe emission levels of CO, other major pollutants, and fuel economy. The EPA Greenhouse Gas Score reflects CO2 emissions and is based on the vehicle fuel economy. As less fuel is burned, less CO2 is emitted. The Greenhouse Gas Score varies by fuel type and is based on the carbon content of the fuel used and the fuel economy of the engine. City fuel economy and highway fuel economy from the grams/mile values for total HC, CO, CO2 and, where applicable, CH3, OH, HCHO, NMHC and CH4 (in accordance with 40 CFR 86.08426(a)(6)(iii) or 40 CFR 86.1837-01). Also there are tests for fuel specific gravity, carbon weight fraction, net heating value, and additionally for natural gas. For gasoline-fueled automobiles, the fuel economy in miles per gallon is to be calculated using the following equation:mpg=(5174×10\4\×CWF×SG)/[((CWF×HC)+(0.429×CO)+(0.273×C02))×((0.6×SG×NHV)+5471)]
Similar calculations are used for diesel-fueled automobiles, methanol-fueled automobiles, automobiles designed to operate on mixtures of fuels, and automobiles designed to operate on natural gas fuels.
According to the Office of Transportation and Air Quality, the EPA “Inventory of U.S. Greenhouse Gas Emissions and Sinks”, and EPA Publication EPA420-F-05-001 February 2005, there is an estimated CO2 emissions from fuel, from the heat content of the fuel, and carbon content coefficients in terms of carbon content per quadrillion BTU (QBTU), using Energy Information Administration data. The estimates are based only on average carbon content of conventional gasoline and diesel fuels and do not address the impact of fuel additives. The Intergovernmental Panel on Climate Change (IPCC) calculations require an oxidation factor be applied to the carbon content to account for the small porlion of fuel that is not oxidized into CO2. All oil and oil products, the oxidation factor used is 0.99, that is, the factor is used as assuming 99% of carbon in the fuel is eventually oxidized. Therefore, the CO2 emissions for the above mentioned fuels is calculated:CO2 emissions from a gallon of gasoline: 2,421 g×0.99×(44/12)=8,788 g=8.8 kg/gallon=19.4 pounds/gallonCO2 emissions from a gallon of diesel=2,778 g×0.99×(44/12)=10,084 g=10.1 kg/gallon=22.2 pounds/gallon
In 1990, the U.S. Environmental Protection Agency (EPA) estimated that the average sulfur content of on-highway diesel fuel is approximately 0.25% by weight and required this level be reduced to no more than 0.05% by weight by Oct. 1, 1993. The EPA also required that this diesel fuel have a minimum cetane index specification of 40 (or meet a maximum aromatics level of 35%). The objective of this rule was to reduce sulfate particulate and carbonaceous and organic particulate emissions (Federal Register, Vol. 55, No. 162, Aug. 21, 1990, pp. 34120-34151). Diesel fuel natural impurities and chemical composition can damage operation of emission control devices and increase pollutant formation in the atmosphere. The U.S. Environmental Protection Agency established low sulfur requirements in diesel fuel beginning in 2006. (EPA420-F-05-029, July 2000). Low-sulfur diesel fuels and technology for meeting these emission were not commercially implemented, however the U.S. Environmental Protection Agency and its Smartway Program recognized exemplary trucking companies on Oct. 30, 2006 American Trucking Association Annual Conference in Grapevine, Texas for improving aerodynamics and exhaust after-treatment devices which can reduce fleet fuel consumption, fuel costs and help reduce CO2 emissions pollution. Also, in 1998, the California Air Resources Board (CARB) declared all light trucks, some mini-vans, and all diesel-powered vehicles must meet the same standard beginning in 2004. The diesel manufacturers improved fuel economy gains but did not meet the more stringent tailpipe standards. (L. Brooke, Automotive Industries, December 1998; Gale Group 2000)
The EPA states that another way to calculate the greenhouse gas impact of each vehicle includes full fuel life cycle estimates, that is to consider all the steps in the creation, consumption of fuel, from production and refining to distribution and final use (US EPA Green Vehicle Guide). Another group that specifies, reports and trades with industrial 15 applications that involve gases is based on the Kyoto Protocol which opened a market based solution for climate change mitigation that includes carbon dioxide emission trading. Some countries are passive to trading energy and forestry commodities (“Carbon dioxide emission trading, or not? An institutional analysis of company behaviour in Sweden”, Corporate Social Responsibility and Environmental Management, Wiley, Volume 11, Issue 4, pages 211-221, December 2004, article first published online 16 Nov. 2004).
Discussions have been published for reducing emissions of CO2 represents an essentially permanent benefit for the atmosphere while capturing CO2 that is produced represents the future challenge of storing and risk of escape to the atmosphere or marketing a dubious output. (G. Marland “Trading permanent and temporary carbon emission credits, Abstract, Journal of Earth and Environmental Science.) Conditions for optimizing combined cooling, heating, and operational costs of power systems generally focuses only on energy cost. (H. Cho, Evaluation of CCHP systems performance based on operational cost, primary energy consumption, and carbon dioxide emission by utilizing an optimal operation scheme, Dept. of Mechanical Engr. Mississippi State University, Elsevier, available online 13 May 2009)
U.S. Pat. No. 5,376,154 discloses low-sulfur diesel fuels containing organometallic complexes related to low-sulfur diesel fuels for diesels equipped the exhaust traps. Generally temperatures of approximately 450-600° C. are required for exhaust temperatures to prevent an accumulation of carbon black and plugs in the traps.
Many examples of organometallic complexes derived from variations of combinations including aromatics, aldehdyes, ketones, amines, and thiol-containing aromatics are cited, and occur at lower temperatures than the heated traps. It also has been suggested that the particle build-up in the traps can be controlled by lowering the ignition temperature of the particulates so that the particles begin burning at the lowest possible temperatures. One method of lowering the ignition temperature involves the addition of a combustion improver to the exhaust particulate, and the most practical way to effect the addition of the combustion improver to the exhaust particulate is by adding the combustion improver to the fuel. Copper compounds have been suggested as combustion improvers for fuels including diesel fuels.
U.S. Pat. No. 6,858,047 discloses a fuel additive for gasoline and diesel engines, which includes lithium didodecylbenzenesulfonate, t-butyl perbenzoate, and methyl ethyl ketone peroxide in a solvent such as diphenyl for an aesthetically pleasing product and for better mileage for internal combustion engines.
U.S. Pat. No. 5,023,016 discloses a concentrate composition comprising (a) a blend of (i) a metal sulfonate and (ii) an alkali or alkaline earth metal or zinc salt of a carboxylic acid and (b) a carrier. The composition is useful as a rust- and corrosion-inhibitor in a petroleum or synthetic base medium and is capable of maintaining metal sulfonate content at temperatures greater than 150° C., e.g., 200° C., for 20 hours. Sodium, potassium, alkali metal salts of difunctional arylsulfonic acids have been used as fuel additives.
U.S. Pat. Appl. US2007/025355 A1 discloses many compositions for fuel additives and the inventor reports vehicle emissions data as fuel economy mileage measurements.
U.S. Pat. No. 4,002,558 discloses the use of inorganic halides to reduce undesirable haze or emulsion in distillate fuels and in diesel fuels due to slight traces of water.
International Publication No. WO 03/040269A I discloses a wide variety of compounds and metals that may be considered combustion enhancers to be placed in solvents and added to most fuel types, as defined by the authors.
U.S. Pat. No. 4,612,880 discloses a method of operating an internal combustion engine by introducing an additive, which inhibits the formation of engine deposits by addition of an oil soluble cyclopentadienyl iron compound, which is stable and available, and carboxylic acids/esters, which are free of heteroatoms. The manifold and/or combustion surfaces have a combined thermal conductance and thermal penetration allowing the surface temperatures to be higher than those temperatures at which deposits form (about 400° C. and above) and simultaneously storing or generating insufficient heat during the next repeated process.